CN115443559A - Cathode material, preparation method thereof, electrochemical device and electronic device - Google Patents
Cathode material, preparation method thereof, electrochemical device and electronic device Download PDFInfo
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- CN115443559A CN115443559A CN202180030956.4A CN202180030956A CN115443559A CN 115443559 A CN115443559 A CN 115443559A CN 202180030956 A CN202180030956 A CN 202180030956A CN 115443559 A CN115443559 A CN 115443559A
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- electrode material
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- silicon
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- 239000010406 cathode material Substances 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 108
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 55
- 239000010703 silicon Substances 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
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- 238000000034 method Methods 0.000 claims description 34
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- 238000012935 Averaging Methods 0.000 description 2
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- 229910013075 LiBF Inorganic materials 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a negative electrode material, a preparation method of the negative electrode material, an electrochemical device and an electronic device, wherein the negative electrode material comprises a porous carbon fiber framework and a silicon-based material filled in the porous carbon fiber framework; wherein, the diameter of porous carbon fiber skeleton is 0.5um to 5um, just the slenderness ratio of porous carbon fiber skeleton is 5 to 100. The cathode material provided by the application can effectively relieve the expansion of the cathode caused by the expansion of silicon base and graphite, thereby improving the cycle performance of the cathode material.
Description
The present disclosure relates to the field of negative electrode materials, and more particularly, to a negative electrode material, a method of preparing the same, an electrochemical device, and an electronic device.
At present, the silicon-based negative electrode material has a gram capacity of 1500mAh/g to 4200mAh/g, and is considered to be the next generation lithium ion negative electrode material with the most application prospect. But low conductivity of silicon: (>10 8 Ω. Cm), and which has a volume expansion of about 300% during charge and discharge and generates an unstable solid electrolyte interface film (SEI), a silicon negative electrode material being chargedCan pulverize and drop from the mass flow body in the discharge process for lose the electric touch between active material and the mass flow body, lead to the electrochemical properties variation, capacity decay, circulation stability descend, hindered its further application to a certain extent. The silicon-based negative electrode material is subjected to nanocrystallization and dispersed in a carbon matrix, so that the cycle performance of the silicon-based negative electrode material can be effectively improved, for example, silicon can be ball-milled to about 100nm by adopting a wet grinding method, and then is subjected to granulation and carbonization with asphalt, polymers and the like, so that the silicon-carbon composite material mainly applied at present is obtained. However, the cycle performance of this negative electrode material is low, and the expansion rate is relatively large.
Content of application
In view of this, the present application provides a negative electrode material, a method for preparing the same, an electrochemical device, and an electronic device, where the negative electrode material can effectively alleviate the expansion of the negative electrode due to the expansion of silicon-based and graphite, thereby improving the cycle performance of the negative electrode material.
In a first aspect, the present application provides a negative electrode material, including a porous carbon fiber skeleton and a silicon-based material filled in the porous carbon fiber skeleton; wherein, the diameter of porous carbon fiber skeleton is 0.5um to 5um, just the slenderness ratio of porous carbon fiber skeleton is 5 to 100.
In one possible embodiment, in combination with the first aspect, the negative electrode material further includes a carbon layer.
In a possible embodiment in combination with the first aspect, the carbon layer has a thickness of 1nm to 100nm.
With reference to the first aspect, in one possible embodiment, the anode material satisfies at least one of the following conditions (1) to (4):
(1) The mass percentage content of silicon in the negative electrode material is 5-50%;
(2) The mass percentage content of carbon in the negative electrode material is 50-95%;
(3) The specific surface area of the negative electrode material is less than 50m 2 /g；
(4) The negative electrode material has a powder true density of 2.0gcm 3 To 2.3g/cm 3 。
In a possible embodiment, in combination with the first aspect, in an X-ray diffraction pattern, the highest intensity value of a diffraction peak attributed to 28.4 DEG +/-0.2 DEG is M, and the highest intensity value of a diffraction peak attributed to 45 DEG +/-0.5 DEG is N, wherein M/N is more than or equal to 1.
In a second aspect, embodiments of the present application provide a method for preparing an anode material, the method including the steps of:
dispersing a pore-foaming agent and acrylonitrile in dimethylacrylamide to form a mixed solution;
preparing the mixed solution into polymeric fibers of 0.2um to 10um through a spinning process;
carbonizing, crushing and acid-washing the polymer fiber to obtain a porous carbon fiber skeleton, wherein the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the length-diameter ratio of the porous carbon fiber skeleton is 5 to 100;
introducing silicon source gas into the porous carbon fiber skeleton, and performing primary vapor deposition to obtain a silicon-loaded carbon fiber material;
and introducing carbon source gas into the silicon-loaded carbon fiber material, and performing secondary vapor deposition to obtain the cathode material.
In a third aspect, the present application provides a negative electrode sheet, including a negative electrode current collector and a negative electrode active material layer disposed on a surface of the negative electrode current collector, where the negative electrode active material layer includes the negative electrode material described in the first aspect or the negative electrode material prepared by the negative electrode material preparation method described in the second aspect.
In a fourth aspect, the present application provides an electrochemical device comprising a negative electrode active material layer, wherein the negative electrode active material layer comprises the negative electrode material of the first aspect or the negative electrode material prepared by the negative electrode material preparation method of the second aspect.
In combination with the fourth aspect, in one possible embodiment, the electrochemical device is a lithium ion battery.
In a fifth aspect, the present application provides an electronic device comprising the electrochemical device of the fourth aspect.
Compared with the prior art, the method has the following beneficial effects:
the application provides a negative electrode material, size and porous carbon fiber skeleton's draw ratio through control porous carbon fiber skeleton, deposit silicon-based material to porous carbon fiber skeleton, utilize porous carbon fiber skeleton as negative electrode material's support skeleton, certain volume inflation can be alleviated to porous carbon fiber skeleton's inside hole, and fibrous support skeleton can effectively increase silicon-based negative electrode material's long-range electrical contact for granular carbon skeleton, can effectively alleviate because silicon-based material leads to the inflation of negative pole with graphite inflation, thereby improve negative active material's cyclicity.
While the following is a preferred embodiment of the embodiments of the present application, it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the embodiments of the present application, and such improvements and modifications are also considered to be within the scope of the embodiments of the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value may, as its lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" means "a plurality of" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
In a first aspect, an embodiment of the present application provides a negative electrode material, where the negative electrode material includes a porous carbon fiber skeleton and a silicon-based material filled in the porous carbon fiber skeleton; wherein, the diameter of porous carbon fiber skeleton is 0.5um to 5um, just the slenderness ratio of porous carbon fiber skeleton is 5 to 100.
The application provides a negative electrode material, size and porous carbon fiber skeleton's draw ratio through control porous carbon fiber skeleton, deposit silicon-based material to porous carbon fiber skeleton, utilize porous carbon fiber skeleton as negative electrode material's support skeleton, certain volume inflation can be alleviated to porous carbon fiber skeleton's inside hole, and fibrous support skeleton can effectively increase silicon-based negative pole's long-range electrical contact for granular skeleton, can effectively alleviate because silicon-based material leads to the inflation of negative pole with the graphite inflation, thereby improve negative active material's cyclicity ability.
As an optional technical solution of the present application, the diameter of the porous carbon fiber skeleton may specifically be 0.5um, 0.7um, 1.4um, 1.5um, 1.6um, 3.2um, 5.0um, etc., and may also be other values within the above range, which is not limited herein. The aspect ratio of the porous carbon fiber skeleton may specifically be 5, 5.5, 6.4, 6.6, 6.9, 7.0, 8.0, 12.8, 13, 20, 50, or 100, and may be other values within the above range, which is not limited herein. When the diameter of the porous carbon fiber skeleton is too large, the length-diameter ratio is too small, the contact sites of the silicon composite material and graphite are few due to the too small length-diameter ratio, and the electrical contact failure of silicon and graphite is easily caused in the silicon expansion process, so that the cycle performance of the battery cell is deteriorated.
As an optional technical scheme of the application, in an X-ray diffraction spectrum of the cathode material, the highest intensity value of a diffraction peak belonging to 28.4 +/-0.2 degrees is M, and the highest intensity value of a diffraction peak belonging to 45 +/-0.5 degrees is N, wherein M/N is more than or equal to 1.
The diffraction peak at around 28.4 ° is a diffraction peak formed by silicon fine particles of crystalline silicon, and the diffraction peak at around 45 ° is a diffraction peak formed by carbon; the peak growth of silicon is limited by taking the peak of carbon as a reference.
As an optional technical solution of the present application, the negative electrode material further includes a carbon layer, and a thickness of the carbon layer is 1nm to 100nm. Understandably, the carbon layer is too thick, the lithium ion transmission efficiency is reduced, the high-rate charge and discharge of the material are not facilitated, the comprehensive performance of the negative electrode material is reduced, the carbon layer is too thin, the electrical conductivity of the negative electrode material is not facilitated to be increased, the volume expansion inhibition performance of the material is weak, and the long cycle performance is poor.
Alternatively, the carbon layer may have a thickness of 1nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 100nm, or the like, or may have other values within the above range, which is not limited herein.
As an optional technical scheme of the application, the content of the silicon element in the negative electrode material is 5-50% by mass; specifically, the content may be 5%, 15%, 20%, 25%, 30%, 40%, or 50%, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable. The silicon content is too high, the volume expansion rate of the lithium ion battery is increased, and the improvement of the cycle stability is not facilitated; the content of silicon element is too low, which affects the first effect and rate capability of the lithium ion battery.
As an optional technical scheme of the present application, the content of the carbon element in the negative electrode material is 50% to 95% by mass; specifically, it may be 50%, 55%, 60%, 65%, 70%, 80%, or 95%, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable. The carbon content is too high, the lithium ion transmission efficiency is reduced, the high-rate charge and discharge of the material are not facilitated, the comprehensive performance of the negative electrode material is reduced, the carbon content is too low, the conductivity of the negative electrode material is not facilitated to be increased, the volume expansion inhibition performance of the material is weak, and the price difference of the long-cycle performance is caused.
As an optional technical scheme of the application, the specific surface area of the negative electrode material is less than 50m 2 (iv) g; it may be 1.50m 2 /g、2.00m 2 /g、5.0m 2 /g、10.0m 2 /g、15m 2 /g、20m 2 /g、30m 2 G or 40m 2 And/g, but not limited to, the recited values, and other unrecited values within the range are equally applicable. The specific surface area of the negative electrode material is in the range, so that the processing performance of the material is ensured, the first efficiency of a lithium battery made of the negative electrode material is improved, and the cycle performance of the negative electrode material is improved. Preferably, the specific surface area of the anode material is 2.6m 2 G to 28m 2 Per gram, and further preferably, the specific surface area of the negative electrode material is 2.6m 2 G to 5.2m 2 /g。
As an optional technical scheme of the application, the powder true density of the negative electrode material is 2.0g/cm 3 To 2.3g/cm 3 . Specifically, it may be 2.0g/cm 3 、2.05g/cm 3 、2.1g/cm 3 、2.15g/cm 3 、2.2g/cm 3 、2.25g/cm 3 Or 2.3g/cm 3 And the like, but are not limited to the recited values, and other unrecited values within the numerical range are equally applicable. The true density of the negative electrode material is in the range, which is beneficial to improving the energy density of a lithium battery made of the negative electrode material. The powder true density is obtained by placing a powder sample with a certain mass in a true density tester, sealing a test system, introducing helium or nitrogen according to a program, and calculating the true volume according to the Bohr's law by testing the pressure of gas in a sample chamber and an expansion chamber.
In a second aspect, the present application provides a method for preparing an anode material, the method comprising the steps of:
dispersing a pore-foaming agent and acrylonitrile in dimethylacrylamide to form a mixed solution;
preparing the mixed solution into polymeric fibers of 0.2um to 10um through a spinning process;
carbonizing, crushing and acid-washing the polymer fiber to obtain the porous carbon fiber skeleton, wherein the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the length-diameter ratio of the porous carbon fiber skeleton is 5 to 100;
introducing silicon source gas into the porous carbon fiber skeleton, and performing primary vapor deposition to obtain a silicon-loaded carbon fiber material;
and introducing carbon source gas into the silicon-loaded carbon fiber material, and performing secondary vapor deposition to obtain the cathode material.
In the above scheme, silicon is deposited into the porous carbon fiber skeleton in a mode of thermal decomposition of silicon source gas, the fibrous carbon skeleton can effectively increase the long-range electrical contact of the silicon-based negative electrode material relative to the granular carbon skeleton, the expansion of the negative electrode caused by the expansion of silicon-based and graphite can be effectively relieved, and the cycle performance of the negative electrode active material can be effectively improved.
The preparation method is specifically described by combining the following embodiments:
and S10, dispersing the pore-foaming agent and the acrylonitrile in the dimethylacrylamide to form a mixed solution.
In a specific embodiment, the pore-foaming agent is calcium carbonate, and the particle size of the calcium carbonate particles is 10nm to 20nm. Specifically, it may be 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm or 20nm, but it may be other values within the above range. The particle size of the pore-foaming agent is controlled, so that the pore-foaming agent can be adhered to the polymer fiber, and then the porous structure is formed through acid washing treatment.
As an alternative technical scheme, the molecular weight of the acrylonitrile is 100w to 1000w; specifically, the amount may be 100w, 150w, 200w, 300w, 400w, 500w, 600w, 700w, 800w, 1000w, or the like, but may be other values within the above range.
And S20, preparing the mixed solution into the polymeric fiber of 0.2um to 10um through a spinning process.
As an optional technical solution of the present application, the spinning process includes at least one of electrospinning, liquid-phase spinning, and melt spinning.
And S30, carbonizing, crushing and acid washing the polymer fibers to obtain the porous carbon fiber skeleton, wherein the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the length-diameter ratio of the porous carbon fiber skeleton is 5 to 100.
By controlling the length-diameter ratio of the porous carbon fiber material, the long-range electrical contact of the silicon-based negative electrode material can be effectively increased, the expansion of the negative electrode caused by the expansion of silicon and graphite can be effectively relieved, and the cycle performance of the negative electrode active material can be effectively improved.
Specifically, the step of the carbonization treatment includes:
and (2) oxidizing the polymer fiber in air at 200-300 ℃ for 2-10 h, and then carbonizing the polymer fiber at 600-1200 ℃ for 2-12 h in an argon environment.
In the oxidation process, the acrylonitrile can generate a ring forming reaction, which is beneficial to forming a more stable carbon fiber material after heat treatment.
In the high-temperature carbonization process, the polymer fibers are carbonized to form carbon fibers, and the carbon fibers can be used as a skeleton structure of the negative active material, so that the cycle stability of the negative active material can be improved.
As an optional technical scheme, the crushing treatment comprises at least one of ball milling, wet sand milling or high-speed air flow milling. It will be appreciated that the crushing process can result in carbon fibre materials of different lengths, thereby controlling the aspect ratio of the porous carbon fibre skeleton.
As an optional technical scheme of the application, the acid solution adopted by the acid cleaning treatment is hydrochloric acid or hydrofluoric acid. It is understood that hydrochloric acid or hydrofluoric acid can react with the porogen attached to the carbon fibers such that the porogen can be dissolved in the hydrochloric acid or hydrofluoric acid such that the carbon fibers form a pore structure. In this embodiment, since the porogen is a nano-scale particle, the pore structure formed on the carbon fiber is also nano-scale.
S40, introducing silicon source gas into the porous carbon fiber skeleton, and performing primary vapor deposition to obtain a silicon-loaded carbon fiber material;
the method has the advantages that one-time vapor deposition is silicon deposition, silicon is deposited in the carbon fiber framework to form nano silicon, the pore structure of the carbon fiber is also in a nano level, so that the silicon gathering area on the carbon fiber framework can be effectively controlled to be below 20nm, and the volume expansion of the silicon can be relieved by the nano pore structure, so that the cycle performance of the silicon-based material is improved. In this embodiment, the silicon source gas is silane.
As an alternative solution of the present application, the deposition temperature of the first vapor deposition is 500 ℃ to 900 ℃, specifically 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 800 ℃, or 900 ℃, or the like, and may be other values within the above range.
As an optional technical solution of the present application, the deposition time of the first vapor deposition is 0.25h to 24h; specifically, the average particle size may be 0.25h, 0.5h, 1h, 2h, 3h, 6h, 8h, 12h, 16h, 18h, 24h, or the like, but may be other values within the above range.
And S50, introducing a carbon source gas into the silicon-loaded carbon fiber material, and performing secondary vapor deposition to obtain the cathode material.
As an alternative embodiment of the present application, the carbon source gas includes at least one of methane, acetylene, propane, or ethylene.
As an alternative solution of the present application, the deposition temperature of the second vapor deposition is 500 ℃ to 950 ℃, specifically 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 800 ℃, 900 ℃, or 950 ℃, and the like, and may be other values within the above range.
As an optional technical scheme of the application, the deposition time of the secondary vapor deposition is 0.5h to 12h; specifically, the average particle size may be 0.5h, 1h, 2h, 3h, 6h, 8h, 10h, 12h, or the like, but may be other values within the above range.
In a third aspect, an embodiment of the present application provides a negative electrode tab, where the negative electrode tab includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, and the negative electrode active material layer includes a negative electrode material according to the first aspect of the present application.
As an alternative solution, the negative active material layer includes a binder, and the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1,1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like, which is not limited herein.
As an alternative solution of the present application, the negative active material layer further includes a conductive material, and the conductive material includes natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel, aluminum, silver, or a polyphenylene derivative, and the like, which is not limited herein.
As an alternative solution, the negative electrode current collector includes, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, or a polymer substrate coated with a conductive metal.
In a fourth aspect, the present application further provides an electrochemical device, including a negative electrode active material layer, where the negative electrode active material layer includes the negative electrode material described in the first aspect or the negative electrode material prepared by the negative electrode material preparation method described in the second aspect.
As an optional technical solution of the present application, the electrochemical device further includes a positive electrode sheet, and the positive electrode sheet includes a positive current collector and a positive active material layer located on the positive current collector.
As an optional technical solution of the present application, the positive electrode active material includes at least one of lithium cobaltate (LiCoO 2), a lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium iron manganese phosphate, and lithium manganese.
As an alternative solution, the positive active material layer further includes a binder and a conductive material. As can be appreciated, the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
Specifically, the binder includes at least one of polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymer, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1,1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy, or nylon.
Specifically, the conductive material includes a carbon-based material, a metal-based material, a conductive polymer, and a mixture thereof. In some embodiments, the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
As an alternative solution, the positive electrode current collector includes, but is not limited to: aluminum foil.
As an alternative solution, the electrochemical device further includes an electrolyte including an organic solvent, a lithium salt, and an additive.
The organic solvent of the electrolyte according to the present application may be any organic solvent known in the art that can be used as a solvent of the electrolyte. The electrolyte used in the electrolyte according to the present application is not limited, and may be any electrolyte known in the art. The additive of the electrolyte according to the present application may be any additive known in the art as an additive of electrolytes.
In particular embodiments, the organic solvents include, but are not limited to: ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate or ethyl propionate.
In a particular embodiment, the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt.
In particular embodiments, the lithium salt includes, but is not limited to: lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium difluorophosphate (LiPO) 2 F 2 ) Lithium bis (trifluoromethanesulfonylimide) LiN (CF) 3 SO 2 ) 2 (LiTFSI), lithium bis (fluorosulfonyl) imide Li (N (SO) 2 F) 2 ) (LiFSI), lithium bis (oxalato) borate LiB (C) 2 O 4 ) 2 (LiBOB) or lithium difluorooxalato borate LiBF 2 (C 2 O 4 )(LiDFOB)。
In a specific embodiment, the concentration of the lithium salt in the electrolyte may be 0.5 to 3mol/L.
As an alternative solution, the electrochemical device of the present application includes, but is not limited to: all kinds of primary batteries, secondary batteries, fuel cells, solar cells or capacitors.
In a specific embodiment, the electrochemical device is a lithium secondary battery, wherein the lithium secondary battery includes, but is not limited to: a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
In a fifth aspect, embodiments of the present application further provide an electronic device, which includes the electrochemical device according to the fourth aspect.
As an optional technical solution of the present application, the electronic device includes, but is not limited to: a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a cellular phone, a portable facsimile machine, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a portable cleaner, a portable CD player, a mini-disc, a transceiver, an electronic organizer, a calculator, a memory card, a portable recorder, a radio, a backup power supply, a motor, an automobile, a motorcycle, a power-assisted bicycle, a lighting apparatus, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large-sized household battery or a lithium ion capacitor, and the like.
The preparation of lithium ion batteries is described below by taking lithium ion batteries as an example and combining specific examples, and the method is in the field
The skilled person will appreciate that the preparation methods described in the present application are only examples and that any other suitable preparation method is within the scope of the present application.
1. Preparation of negative electrode material
Dispersing calcium carbonate with the particle size of 10nm to 20nm and acrylonitrile in dimethylacrylamide to form a mixed solution;
preparing the mixed solution into polymeric fibers of 0.2um to 10um through a spinning process;
oxidizing the polymer fiber in air at 250 ℃ for 5h, then carbonizing at high temperature, sintering at 1000 ℃ for 8h under inert atmosphere, and then crushing and pickling to obtain a porous carbon fiber skeleton;
introducing silane gas into the porous carbon fiber skeleton, and performing primary vapor deposition, wherein the deposition temperature is controlled to be 500-900 ℃, and the deposition time is controlled to be 0.25-24 h, so as to obtain the silicon-loaded carbon fiber material;
and introducing ethylene gas into the silicon-loaded carbon fiber material, and performing secondary vapor deposition, wherein the deposition temperature is controlled to be 500-950 ℃, and the deposition time is controlled to be 0.5-12 h, so as to obtain the cathode material, wherein the thickness of the carbon layer is 1-100 nm.
Examples 1 to 9 were prepared according to the above method, and the specific parameters of examples 1 to 9 are shown in table 1 below.
Further, comparative example 1 was prepared according to the above method, the aspect ratio of the prepared porous carbon fiber skeleton of comparative example 1 was 1.0, and specific parameters of comparative example 1 are shown in table 1 below.
Further, comparative example 2 was prepared according to the above-described method, and in the preparation process of comparative example 2, the mixed solution was not made into a polymeric fiber by a spinning process, but made into a block polymer, and the carbon skeleton in the prepared anode material was spherical. Specific parameters of comparative example 2 are shown in table 1 below.
TABLE 1 carbon skeleton Performance parameters
2. Performance test of the anode material:
(1) And (3) observing the microscopic morphology of the powder particles of the negative electrode material:
observing and characterizing the surface condition of the material by using a scanning electron microscope to perform powder micro-morphology, wherein the selected test instrument is as follows: oxFORD EDS (X-max-20 mm) 2 ) The focal length is adjusted by the accelerating voltage of 10KV, the observation times are from 50K for high-power observation, and the particle agglomeration condition is mainly observed at low power of 500-2000.
(2) Diameter test method of porous carbon fiber skeleton:
selecting 20 fibers randomly by adopting SEM, testing the directness and the length of the fibers to obtain the length and the length of each fiber, averaging the diameters of the fibers to obtain the diameter of the fibers, averaging the lengths to obtain the length of the fibers, and comparing the diameters with each other to obtain the length-diameter ratio of the fibers.
(3) The method for testing the silicon content in the negative electrode material comprises the following steps:
weighing 0.05 to 0.1g of sample, adding 1.2 to 1.5g of dry potassium hydroxide into the sample, putting the sample into a muffle furnace at 400 ℃, cooling the sample, adding boiling water to soak the sample, repeatedly washing the sample to be dry, filtering the sample solution by using medium-speed filter paper into a 100mL PP bottle, diluting the sample solution by 100 times, testing the diluent by adopting ICP-OES, and calculating the silicon content of the sample.
(4) The method for testing the specific surface area of the negative electrode material comprises the following steps:
after the adsorption amount of the gas on the solid surface at different relative pressures is measured at constant temperature and low temperature, the adsorption amount of the monolayer of the sample is obtained based on the Bronuore-Eltt-Taylor adsorption theory and the formula (BET formula) thereof, and the specific surface area of the solid is calculated.
About 1.5g to 3.5g of the powder sample was weighed into a test sample tube of TriStar II 3020, degassed at about 200 ℃ for 120min and tested.
(5) The method for testing the true density of the negative electrode material comprises the following steps:
weighing a certain mass of sample (1 g to 5 g), placing the sample in a true density tester, sealing a testing system, and introducing helium or nitrogen according to a program. The true density is calculated by testing the pressure of the gas in the sample and expansion chambers and calculating the true volume according to Bohr's law (PV = nRT).
(6) The method for testing the carbon content in the negative electrode material comprises the following steps:
the sample is heated and combusted at high temperature by a high-frequency furnace under the condition of oxygen enrichment to oxidize carbon and sulfur into carbon dioxide and sulfur dioxide, the gas enters a corresponding absorption cell after being treated, corresponding infrared radiation is absorbed, and then the infrared radiation is converted into corresponding signals by a detector. The signal is sampled by a computer, is converted into a numerical value in direct proportion to the concentration of carbon dioxide and sulfur dioxide after linear correction, then the value of the whole analysis process is accumulated, after the analysis is finished, the accumulated value is divided by a weight value in the computer, and then multiplied by a correction coefficient, and blank is deducted, thus the percentage content of carbon and sulfur in the sample can be obtained. The sample was tested using a high frequency infrared carbon sulfur analyzer (Shanghai DE Ky HCS-140).
(7) X-ray diffraction testing of the negative electrode material:
weighing 1.0-2.0 g of a sample, pouring the sample into a groove of a glass sample rack, compacting and grinding the sample by using a glass sheet, testing by using an X-ray diffractometer (Bruk, D8) according to JJS K0131-1996 'general rule on X-ray diffraction analysis method', setting the testing voltage at 40kV, setting the current at 30mA, setting the scanning angle at 10-85 DEG, the scanning step length at 0.0167 DEG, setting the time at each step length at 0.24s, obtaining an XRD diffraction pattern of the cathode material, obtaining the highest intensity value M of the 2 theta in the XRD diffraction pattern, belonging to 28.4 DEG, and the highest intensity value N of the 2 theta in the XRD diffraction pattern, and calculating the ratio of M/N.
3. Preparation of lithium batteries
(1) Preparation of the Positive electrode
The positive electrode active material lithium cobaltate (LiCoO) 2 ) Conductive carbon black and a binder polyvinylidene fluoride according to a weight ratio of 95:2.5:2.5, adding N-methyl pyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain anode slurry; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil; and drying the aluminum foil, then carrying out cold pressing, cutting and slitting, and drying under a vacuum condition to obtain the positive plate.
(2) Preparation of the negative electrode
The negative electrode material, graphite, and conductive agent (conductive carbon black, super) of the above examples and comparative examples were mixed
) And binder PAA in a weight ratio of 70:15:5:10, mixing, adding deionized water, and obtaining cathode slurry under the action of a vacuum stirrer; uniformly coating the negative electrode slurry on a copper foil of a negative electrode current collector; and drying the copper foil, then carrying out cold pressing, cutting and slitting, and drying under a vacuum condition to obtain the negative plate.
(3) Electrolyte solution
In a dry argon atmosphere glove box, liPF6 was added to a solvent in which Propylene Carbonate (PC), ethylene Carbonate (EC), and diethyl carbonate (DEC) were mixed (weight ratio about 1.
(4) Isolation film
The polyethylene porous polymer film is used as a separation film.
(5) Preparation of lithium ion battery
Stacking the anode, the isolating film and the cathode in sequence to enable the isolating film to be positioned between the anode sheet and the cathode sheet to play an isolating role, and then winding to obtain a bare cell; and (3) after welding the lug, placing the bare cell in an outer packaging foil aluminum-plastic film, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, capacity test and other procedures to obtain the lithium ion battery.
4. And (3) testing the performance of the lithium battery:
(1) Lithium ion battery cycle performance test
And (3) placing the lithium ion battery in a constant temperature box with the temperature of 45 ℃ (25 ℃), and standing for 30 minutes to keep the temperature of the lithium ion battery constant. And charging the lithium ion battery reaching the constant temperature to the voltage of 4.4V at a constant current of 0.7C, then charging the lithium ion battery to the current of 0.025C at a constant voltage of 4.4V, standing for 5 minutes, discharging the lithium ion battery to the voltage of 3.0V at a constant current of 0.5C, taking the capacity obtained in the step as the initial capacity, performing a cyclic test on the charge of 0.7C/discharge of 0.5C, and taking the ratio of the capacity of each step to the initial capacity to obtain a capacity fading curve. The cycle number of the battery with the capacity retention rate of 90% after the cycle at 25 ℃ is recorded as the room-temperature cycle performance of the battery, the cycle number of the battery with the capacity retention rate of 80% after the cycle at 45 ℃ is recorded as the high-temperature cycle performance of the battery, and the cycle performance of the materials is compared by comparing the cycle number of the two cases.
(2) And (3) testing discharge rate:
and (3) placing the lithium ion battery in a constant temperature box at 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Discharging the lithium ion battery reaching the constant temperature at a constant current of 0.2C until the voltage is 3.0V, standing for 5min, charging at a constant current of 0.5C until the voltage is 4.45V, then charging at a constant voltage of 4.45V until the current is 0.05C, standing for 5min, adjusting the discharge rate, performing discharge tests at 0.2C, 0.5C, 1C, 1.5C and 2.0C respectively to obtain discharge capacities respectively, comparing the capacity obtained at each rate with the capacity obtained at 0.2C, and comparing the rate performance by comparing the ratio of 2C to 0.2C.
(3) And (3) testing the full charge expansion rate of the battery:
the thickness of the fresh battery at half-charge (50% state of charge (SOC)) was measured with a micrometer screw, and when the cycle was 400 cycles, the battery was in a full-charge (100 SOC) state, and the thickness of the battery at this time was measured with the micrometer screw, and compared with the thickness of the fresh battery at initial half-charge (50 SOC), the full-charge (100 SOC) battery expansion rate at this time was obtained.
The performance parameters of the negative electrode materials of examples 1 to 3 and the negative electrode material of comparative example 1 manufactured according to the above-described method are shown in table 1-1, and the performance test results of the lithium batteries manufactured therefrom are shown in table 1-2.
TABLE 1-1
It should be noted that the gram capacity in the table of the present application is the gram capacity of the discharge cut-off voltage of 2.0V;
the first efficiency calculation in the present application table is the capacity at a discharge cutoff voltage of 2.0V/the capacity at a charge voltage cutoff corresponding to 0.005V.
Tables 1 to 2
| Sample(s) | The circulation is cut to 90 percent at 25 DEG C | Circulating to 400 cycles at 25 DEG C | The circulation is cut to 90 percent at the temperature of 45 DEG C | Circulating to 400 cycles at 45 DEG C |
| Number of turns of | Expansion rate of battery | Number of turns of | Expansion rate of battery | |
| Example 1 | 500 | 5.3％ | 420 | 6.0％ |
| Example 2 | 480 | 5.8％ | 390 | 6.2％ |
| Example 3 | 450 | 6.2％ | 380 | 6.9％ |
| Comparative example 1 | 380 | 6.4％ | 350 | 7.2％ |
As can be seen from the test results of examples 1 to 3, when the same type of carbon fiber skeleton is used, the gram capacity of the negative electrode materials of examples 1 to 3 is gradually increased as the content of silicon deposited on the carbon fiber skeleton is increased, and the first efficiency of the battery is also improved. However, the cycle performance of the battery is reduced along with the increase of the silicon content, and the expansion rate of the battery is increased; it follows that the silicon content of the anode material needs to be controlled. Preferably, the silicon content in the anode material is 17.2 to 39 mass%.
In contrast, in comparative example 1, in which spherical carbon skeleton particles were used, the cycle performance of the lithium battery was significantly reduced and the expansion efficiency was significantly increased as compared with examples 1 to 3. This is because the carbon fiber skeleton can effectively increase the long-range electrical contact of the negative electrode material, and can alleviate the expansion of the negative electrode due to silicon and graphite, compared with spherical carbon skeleton particles, thereby improving the cycle performance of the negative electrode material.
The performance parameters of the negative electrode materials of examples 4 to 6 and the negative electrode material of comparative example 1 manufactured according to the above-described method are shown in table 2-1, and the performance test results of the lithium batteries manufactured therefrom are shown in table 2-2.
TABLE 2-1
Tables 2 to 2
From the test results of examples 4 to 6, it can be seen that the diameter of the porous carbon fiber skeleton used in example 4 is 1.5um, the diameter of the porous carbon fiber skeleton used in example 5 is 3.2um, the diameter of the porous carbon fiber skeleton used in example 6 is 5.1um, and the aspect ratio of the porous carbon fiber skeleton used in examples 4 to 6 is in the range of 5.4 to 6.9, and the silicon content and the carbon content of the anode material are similar. It can be seen that when the diameter of the porous carbon fiber skeleton is greater than 5um, the lithium ion battery cyclability is rather decreased. Therefore, the diameter of the porous carbon fiber skeleton should be controlled to 0.5um to 5um.
The performance parameters of the negative electrode materials of examples 7 to 9 and the negative electrode material of comparative example 2 manufactured according to the above-described method are shown in table 3-1, and the performance test results of the lithium batteries manufactured therefrom are shown in table 3-2.
TABLE 3-1
TABLE 3-2
From the test results of examples 7 to 9, it can be seen that when the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the aspect ratio of the porous carbon fiber skeleton is 5 to 100, the lithium ion battery has good cycle performance and rate performance, and a low expansion ratio. Compared with the prior art, the carbon fiber framework adopted in the comparative example 2 has the advantages that when the length-diameter ratio is less than 5, the cycle performance and the rate capability of the lithium ion battery are poor, and the expansion rate is high.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (15)
- The negative electrode material is characterized by comprising a porous carbon fiber skeleton and a silicon-based material filled in the porous carbon fiber skeleton; wherein, the diameter of porous carbon fiber skeleton is 0.5um to 5um, just the slenderness ratio of porous carbon fiber skeleton is 5 to 100.
- The negative electrode material of claim 1, further comprising a carbon layer.
- The anode material according to claim 2, wherein the carbon layer has a thickness of 1nm to 100nm.
- The anode material according to claim 1, characterized in that the anode material satisfies at least one of the following conditions (1) to (4):(1) The mass percentage content of the silicon element in the negative electrode material is 5-50%;(2) The mass percentage content of carbon element in the negative electrode material is 50-95%;(3) The specific surface area of the negative electrode material is less than 50m 2 /g；(4) The negative electrode materialThe powder true density of the material is 2.0g/cm 3 To 2.3g/cm 3 。
- The negative electrode material of claim 1, wherein in an X-ray diffraction pattern, the highest intensity value of a diffraction peak attributed to 28.4 ° ± 0.2 ° is M, and the highest intensity value of a diffraction peak attributed to 45 ° ± 0.5 ° is N, wherein M/N is greater than or equal to 1.
- A method for preparing an anode material, the method comprising the steps of:dispersing a pore-foaming agent and acrylonitrile in dimethylacrylamide to form a mixed solution;preparing the mixed solution into polymeric fibers of 0.2um to 10um through a spinning process;carbonizing, crushing and acid-washing the polymer fiber to obtain a porous carbon fiber skeleton, wherein the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the length-diameter ratio of the porous carbon fiber skeleton is 5 to 100;introducing silicon source gas into the porous carbon fiber skeleton, and performing primary vapor deposition to obtain a silicon-loaded carbon fiber material;and introducing carbon source gas into the silicon-loaded carbon fiber material, and performing secondary vapor deposition to obtain the cathode material.
- The production method according to claim 6, wherein the anode material satisfies at least one of the following conditions (1) to (5):(1) The silicon element in the negative electrode material accounts for 5-50% by mass;(2) The mass percentage content of carbon element in the negative electrode material is 50-95%;(3) The specific surface area of the negative electrode material is less than 50m 2 /g；(4) The powder true density of the negative electrode material is 2.0g/cm 3 To 2.3g/cm 3 ；(5) The carbon layer of the negative electrode material has a thickness of 1nm to 100nm.
- The production method according to claim 6, characterized in that the method satisfies at least one of the following conditions (6) to (7):(6) The deposition temperature of the primary vapor deposition is 500-900 ℃, and the deposition time is 0.25-24 h;(7) The silicon source gas is silane.
- The production method according to claim 6, characterized in that the method satisfies at least one of the following conditions (8) to (9):(8) The deposition temperature of the secondary vapor deposition is 500-950 ℃, and the deposition time is 0.5-12 h;(9) The carbon source gas includes at least one of methane, acetylene, propane, or ethylene.
- The production method according to claim 6, characterized in that the method satisfies at least one of the following conditions (10) to (12):(10) The carbonization treatment condition comprises that the polymer fiber is oxidized in air at 200-300 ℃ for 2-10 h, and then carbonized at 600-1200 ℃ for 2-12 h;(11) The crushing treatment comprises at least one of ball milling, wet sanding or high-speed airflow milling;(12) The acid solution adopted by the acid cleaning treatment is hydrochloric acid or hydrofluoric acid.
- The production method according to claim 6, characterized in that the method satisfies at least one of the following conditions (13) to (15):(13) The pore-foaming agent is calcium carbonate, and the particle size of calcium carbonate particles is 10-20 nm;(14) The molecular weight of the acrylonitrile is 100w to 1000w;(15) The spinning process comprises at least one of electrostatic spinning, liquid phase spinning and melt spinning.
- A negative electrode pole piece comprises a negative electrode current collector and a negative electrode active material layer arranged on the surface of the negative electrode current collector, and is characterized in that the negative electrode active material layer comprises the negative electrode material in any one of claims 1 to 5 or the negative electrode material prepared by the negative electrode material preparation method in any one of claims 6 to 11.
- An electrochemical device comprising a negative electrode active material layer, wherein the negative electrode active material layer comprises the negative electrode material according to any one of claims 1 to 5 or the negative electrode material produced by the negative electrode material production method according to any one of claims 6 to 11.
- The electrochemical device of claim 13, wherein the electrochemical device is a lithium ion battery.
- An electronic device, characterized in that the electronic device comprises the electrochemical device according to claim 13.
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| CN117059765A (en) * | 2023-08-04 | 2023-11-14 | 江门市和创新能源材料有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN117976856A (en) * | 2024-01-16 | 2024-05-03 | 江门市和创新能源材料有限公司 | Silicon-carbon negative electrode material for regular-morphology lithium ion battery and preparation method thereof |
| WO2024183481A1 (en) * | 2023-03-04 | 2024-09-12 | 珠海冠宇电池股份有限公司 | Negative electrode material, negative electrode sheet, and battery |
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| CN116207243B (en) * | 2023-02-22 | 2024-07-16 | 石大胜华新材料集团股份有限公司 | Fibrous silicon-carbon composite material and preparation method thereof |
| CN117096330A (en) * | 2023-10-20 | 2023-11-21 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof, secondary battery and electricity utilization device |
| CN117438558B (en) * | 2023-10-23 | 2024-05-24 | 柔电（武汉）科技有限公司 | Silicon-carbon negative electrode and preparation method thereof |
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